Method for manufacturing nano platinum group high-entropy intermetallic compound through temperature field modulation laser liquid phase corrosion and electro-catalysis application

Abstract

The invention belongs to the technical field of electro-catalysis materials, and particularly relates to a method for manufacturing a nano platinum group high-entropy intermetallic compound through temperature field modulation laser liquid phase corrosion and electro-catalysis application. The preparation method comprises the following steps: mixing at least four metal elements containing platinum group metal elements, transition metal elements and main group metal elements serving as parent materials with a solvent to form a powder suspension or uniformly mixing the parent materials, pressing the mixture into a metal target material and fixing the metal target material in the solvent; and then carrying out laser ablation treatment by adopting a temperature field modulation laser liquid phase corrosion method, so that nano particles are formed under the action of high-energy laser under the modulation of the temperature field, and finally preparing the platinum group nano high-entropy intermetallic compound. The platinum group nano high-entropy intermetallic compound prepared by the method belongs to a multifunctional catalyst, has excellent catalytic performance in the fields of HER, ORR, OR and the like, and can be applied to the field of electrocatalysis.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalytic materials, and particularly relates to a method for manufacturing nano platinum group high-entropy intermetallic compounds by temperature field modulation laser liquid-phase ablation and its electrocatalytic application. Background Art

[0002] With the continuous growth of the global demand for clean energy, the importance of electrocatalytic technology in the fields of energy conversion and storage has become increasingly prominent. Among them, high-entropy intermetallic compounds, as a new type of electrocatalytic material, have attracted extensive attention in the electrocatalytic field in recent years. High-entropy intermetallic compounds combine the advantages of high-entropy alloys and traditional intermetallic compounds, and have unique structures and properties. On the one hand, high-entropy intermetallic compounds are composed of at least four or more metal elements, and their high-entropy effect endows the materials with rich composition components, adjustable electronic structures, and excellent structural stability. On the other hand, traditional intermetallic compounds have an ordered atomic structure, which promotes the separation of active sites and the electronic structure can be regulated, and they are regarded as potential catalysts. Therefore, the ordered atomic structure of high-entropy intermetallic compounds has significant advantages, providing strong support for their application in the electrocatalytic field.

[0003] High-entropy intermetallic compounds have the following advantages in the electrocatalytic field: (1) Multi-element synergistic effect: Through the synergistic effect between multi-metal atoms and the unique ordered atomic configuration of intermetallic compounds, the electronic structure of alloy materials can be more effectively optimized, and further optimize the energy barrier in the electrolytic water hydrogen evolution process. (2) Increase in active sites: High-entropy intermetallic compounds achieve the separation of active sites by maintaining the long-range order of intermetallic compounds and the short-range disorder of high-entropy coordination environments, avoiding the generation of ineffective sites. This separation of active sites enables high-entropy intermetallic compounds to better adsorb reactants in electrocatalytic reactions and promote the progress of the reaction. (3) Adjustable electronic structure: The electronic structure of high-entropy intermetallic compounds is adjustable, making them have higher activity and stability in electrocatalytic reactions.

[0004] However, the current preparation processes of high-entropy intermetallic compounds are mainly methods such as thermal shock or solvothermal methods. Since these methods often require the use of expensive raw materials and complex equipment during the preparation process, the cost is relatively high, and it is difficult to produce on a large scale. Therefore, based on the current situation that most of the preparation methods of high-entropy intermetallic compounds still face considerable challenges in terms of cost and large-scale production, there is an urgent need to develop simpler and more efficient preparation methods to meet the needs of large-scale production. Summary of the Invention

[0005] To overcome the deficiencies of the above-mentioned prior art, the present invention proposes a method for synthesizing nano platinum group high-entropy intermetallic compounds by using temperature field modulated laser liquid-phase ablation technology. The nano platinum group high-entropy intermetallic compounds prepared by this method are a kind of catalytic materials with excellent performance, and have good catalytic activity in the fields of hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and formate oxidation reaction (FOR), and have broad application prospects in the field of electrochemistry.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] In the first aspect of the present invention, a method for manufacturing nano platinum group high-entropy intermetallic compounds by temperature field modulated laser liquid-phase ablation is provided, specifically: using at least four metal elements including platinum group metal elements, transition metal elements and main group metal elements as the parent material, mixing it with a solvent to form a powder suspension or pressing it into a metal target and fixing it in the solvent, and then under the modulation of the temperature field, using the method of laser liquid-phase ablation to perform laser ablation treatment on the micro-nano powder in the suspension or the metal target in the solvent at a constant temperature, so that a plasma plume is formed under the action of temperature field modulated laser liquid-phase ablation, and the plasma plume rapidly condenses due to the rapid quenching effect, and then the platinum group nano high-entropy intermetallic compound is prepared.

[0008] Preferably, the method for manufacturing nano platinum group high-entropy intermetallic compounds by temperature field modulated laser liquid-phase ablation includes the following steps:

[0009] S1. Add at least four metal elements including platinum group metal elements, transition metal elements and main group metal elements into a solvent, and mix them evenly to form a powder suspension; or press at least four metal elements including platinum group metal elements, transition metal elements and main group metal elements into a metal target, and then fix it in the solvent;

[0010] S2. Place the powder suspension or metal target of S1 under a controllable temperature field, and then perform laser ablation treatment on the micro-nano powder in the suspension or the metal target in the solvent at a constant temperature within the range of 20-30 °C to prepare the platinum group nano high-entropy intermetallic compound.

[0011] Since most of the current preparation methods of high-entropy intermetallic compounds still face considerable challenges in terms of cost and large-scale production, the present invention has developed a simpler and more efficient method for preparing nano-high-entropy intermetallic compounds by laser liquid-phase ablation to meet the requirements of large-scale production. At the same time, considering that the pulsed laser will cause instantaneous heating of the liquid in the liquid environment, and the temperature of the liquid will drop during the pulse interval stage, which will lead to severe fluctuations in the temperature of the reaction zone during the continuous laser pulse action without external constant temperature control, and seriously affect the uniformity of the reaction products. Therefore, the present invention suppresses the temperature fluctuations by setting external constant temperature control, thereby effectively optimizing the uniformity of the nanoparticles manufactured by laser liquid-phase ablation, and enabling the prepared high-entropy intermetallic compounds to have excellent catalytic activity.

[0012] More preferably, the platinum group metal elements include palladium (Pd) and platinum (Pt), the transition metal element is copper (Cu), and the main group metal element is indium (In) or tin (Sn) and bismuth (Bi).

[0013] More preferably, the molar ratio of the platinum group metal element, the transition metal element, and the main group metal element is 1-4:1-4:1-4.

[0014] More preferably, the solvent is water or a mixture of an organic solvent and water, and the organic solvent includes isopropanol, ethanol, and acetone.

[0015] More preferably, the particle size of the micro-nano powder in S2 is 10 nm - 1 μm.

[0016] More preferably, the pulsed laser energy required for the laser ablation treatment is 100 μJ - 1000 mJ, the frequency is 1 - 2000 Hz, and the action time is 10 min - 6 h.

[0017] More preferably, the laser ablation treatment uses a 355 nm - 1064 nm nanosecond laser and a 355 nm - 1064 nm laser light guiding system, or a 355 nm - 1064 nm picosecond laser and a 355 nm - 1064 nm laser light guiding system.

[0018] More preferably, the device for controlling the temperature includes a thermocouple monitoring device and a temperature control device, and the temperature control range of the temperature control device is 5 - 60 °C.

[0019] More preferably, when preparing the powder suspension, it is mixed evenly by ultrasonic means, the ultrasonic frequency is 30 - 50 kHz, and the ultrasonic time is 10 - 40 min.

[0020] More preferably, when preparing the powder suspension, the concentration of the suspension is 0.2 - 5 mg / mL.

[0021] The second aspect of the present invention provides a nano platinum group high-entropy intermetallic compound prepared by the preparation method described in the first aspect.

[0022] The nano platinum group high-entropy intermetallic compound prepared by the method of the present invention is a multifunctional electrocatalyst, which has a small overpotential under acidic or alkaline conditions, and has electrocatalytic hydrogen evolution and electrocatalytic oxygen reduction performances comparable to those of platinum-based catalysts. At the same time, it has electrocatalytic formate oxidation performance comparable to that of palladium-based catalysts. Therefore, the method of the present invention can be applied to the preparation of materials with catalytic effects and has wide application value in the catalytic field and the electrochemical field.

[0023] The third aspect of the present invention provides an application of the nano platinum group high-entropy intermetallic compound described in the second aspect in the electrocatalytic field.

[0024] Preferably, the electrocatalytic field includes fields such as HER, ORR, and FOR. The nano platinum group high-entropy intermetallic compound prepared by the present invention is a class of efficient catalysts, which have excellent catalytic activities in fields such as HER, ORR, and FOR, and can be comparable to commercial catalysts.

[0025] Furthermore, the nano platinum group high-entropy intermetallic compound includes an intermetallic compound (PdPtCuIn-HEI) formed by the combination of palladium, platinum, copper, and indium, and can embed intercalated H atoms in the intermetallic compound using isopropanol as a hydrogen source; or includes an intermetallic compound (PdPtCuSeBi-HEI) formed by palladium, platinum, copper, tin, and bismuth.

[0026] Compared with the prior art, the beneficial effects of the present invention are:

[0027] The present invention discloses a method for fabricating nano platinum-group high-entropy intermetallic compounds by temperature-field modulated laser liquid-phase ablation. At least four metal elements including platinum-group metal elements, transition metal elements, and main-group metal elements are used as parent materials. They are mixed with a solvent to form a powder suspension or uniformly mixed and then pressed into a metal target and fixed in the solvent. Then, the micro-nano powder or metal target in the suspension is subjected to laser ablation treatment at a constant temperature by the method of temperature-field modulated laser liquid-phase ablation, so that nano-particles are formed under the action of high-energy laser under temperature-field modulation, and finally platinum-group nano high-entropy intermetallic compounds are prepared. By using the method of the present invention to prepare platinum-group nano high-entropy intermetallic compounds, the composition of the compounds can be adjusted, the metal components can be regulated according to the needs of application scenarios, and the appropriate temperature-field regulation provides a favorable reaction environment, which is conducive to obtaining high-entropy metal nano-particles with better crystallinity and more uniform particle size distribution. In addition, by changing the liquid-phase reaction environment, intercalated H atoms can be embedded in the intermetallic compound structure, which can be used for continuous and large-scale production of nano platinum-group high-entropy intermetallic compounds. At the same time, the prepared products have high consistency, are a series of multifunctional electrocatalysts, have a small overpotential under acidic or alkaline conditions, and have catalytic activity comparable to that of current commercial catalysts. Therefore, the nano platinum-group high-entropy intermetallic compounds prepared by using the method of the present invention have excellent electrocatalytic activity and great application value. Description of the Drawings

[0028] Figure 1 TEM image of nano palladium-platinum-copper-indium high-entropy intermetallic compound (PdPtCuIn-HEI) obtained by reaction under the action of temperature-field modulated laser;

[0029] Figure 2 TEM image of nano palladium-platinum-copper-tin-bismuth high-entropy intermetallic compound (PdPtCuSnBi-HEI) obtained by reaction under the action of temperature-field modulated laser;

[0030] Figure 3 TEM image of nano palladium-platinum-copper-indium high-entropy intermetallic compound (c-PdPtCuIn-HEI) obtained by reaction under the action of laser without temperature-field modulation;

[0031] Figure 4 TEM image of nano silver-platinum-copper-indium high-entropy intermetallic compound (c-AgPtCuIn-HEI) obtained by reaction under the action of temperature-field modulated laser;

[0032] Figure 5 EDS elemental distribution map (Pd, Pt, Cu, In) of nano palladium-platinum-copper-indium high-entropy intermetallic compound (PdPtCuIn-HEI) obtained by reaction under the action of temperature-field modulated laser;

[0033] Figure 6EDS elemental distribution maps (Pd, Pt, Cu, Sn, Bi) of the nano PdPtCuSnBi high-entropy intermetallic compound (PdPtCuSnBi-HEI) obtained by the reaction under the action of a temperature-field modulated laser;

[0034] Figure 7 Electrochemical hydrogen evolution performance diagrams of the nano PdPtCuInH high-entropy intermetallic compound (PdPtCuInH-HEI) and the nano PdPtCuSnBi high-entropy intermetallic compound (PdPtCuSnBi-HEI) obtained by the reaction under the action of a temperature-field modulated laser under acidic conditions (using commercial Pt / C as a control);

[0035] Figure 8 Electrochemical hydrogen evolution performance diagrams of the nano PdPtCuInH high-entropy intermetallic compound obtained by the reaction under the action of a laser with and without temperature-field modulation under acidic conditions;

[0036] Figure 9 Electrochemical oxygen reduction performance diagrams of the nano PdPtCuInH high-entropy intermetallic compound (PdPtCuInH-HEI) and the nano PdPtCuSnBi high-entropy intermetallic compound (PdPtCuSnBi-HEI) obtained by the reaction under the action of a temperature-field modulated laser under alkaline conditions (using commercial Pt / C as a control);

[0037] Figure 10 Electrochemical formate oxidation performance diagrams of the nano PdPtCuInH high-entropy intermetallic compound (PdPtCuInH-HEI) and the nano PdPtCuSnBi high-entropy intermetallic compound (PdPtCuSnBi-HEI) obtained by the reaction under the action of a temperature-field modulated laser under alkaline conditions (using commercial Pd black as a control). Detailed implementation manners

[0038] The following further describes the detailed implementation manners of the present invention. It should be noted here that the description of these implementation manners is used to help understand the present invention, but does not constitute a limitation to the present invention. In addition, the technical features involved in the various implementation manners of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0039] The experimental methods in the following examples are all conventional methods unless otherwise specified, and the test materials used in the following examples can all be obtained through conventional commercial channels unless otherwise specified.

[0040] Example 1: A method for fabricating a nano PdPtCuIn high-entropy intermetallic compound (PdPtCuIn-HEI) by temperature-field modulated laser liquid-phase ablation

[0041] (1) Add 50 mg of high-purity (99.9%) palladium, platinum, copper, and indium powders (particle size 10 nm - 1 μm) to the prepared isopropanol-water mixed solution (volume ratio 3:1) in a molar ratio of 4:1:2:3. The total volume of the solution is 50 mL. Then place the mixed solution in an open container device and ultrasonically disperse it evenly at room temperature for 10 min (ultrasonic frequency 40 kHz).

[0042] (2) Turn on the high-energy laser (Spectra-Physics Laser), use nanosecond lasers with a wavelength of 355 nm and a laser light guiding system. Set the focal length of the plano-convex lens to 500 mm and fix the lens 450 mm directly above the reaction container. Let the high-energy laser perform laser ablation treatment on the mixed solution in the container. The energy of the high-energy nanosecond laser is 100 mJ, the frequency is 50 Hz, and the irradiation time is 1 h. During the laser action, monitor the solution temperature in real time through a thermocouple, and always maintain the temperature rise and fall of the solution through a water cooling device (Shanghai Yushen Instrument Co., Ltd., model DFY-5) (i.e., place the open container device in the water cooling device) so that the temperature always remains at 20 ± 0.2 °C. After the high-energy laser liquid-phase ablation, a nano-palladium-platinum-copper-indium high-entropy intermetallic compound (PdPtCuIn-HEI) is obtained.

[0043] Example 2: A method for fabricating nano-palladium-platinum-copper-tin-bismuth high-entropy intermetallic compound (PdPtCuSnBi-HEI) by temperature field modulated laser liquid-phase ablation

[0044] (1) Thoroughly mix high-purity (99.9%) palladium, platinum, copper, tin, and bismuth micro-nano powder powders in a molar ratio of 2:1:1:2:1, and then press them into a metal target with a diameter of 3 cm and a thickness of 0.5 cm. Fix the metal target at the bottom of the open rotating container device and add 50 mL of water organic solvent.

[0045] (2) Turn on the high-energy laser (Spectra-Physics Laser), use nanosecond lasers with a wavelength of 532 nm and a laser light guiding system. Set the focal length of the plano-convex lens to 500 mm and fix the lens 450 mm directly above the reaction container. Let the high-energy laser perform laser ablation treatment on the mixed solution in the container. The energy of the high-energy nanosecond laser is 800 mJ, the frequency is 10 Hz, and the irradiation time is 180 min. During the laser action, monitor the solution temperature in real time through a thermocouple, and always maintain the temperature rise and fall of the solution through a water cooling device (Shanghai Yushen Instrument Co., Ltd., model DFY-5) (i.e., place the open container device in the water cooling device) so that the temperature always remains at 25 ± 0.2 °C. After the high-energy laser liquid-phase ablation, a nano-palladium-platinum-copper-tin-bismuth high-entropy intermetallic compound (PdPtCuSnBi-HEI) is obtained.

[0046] Comparative Example 1: A method for fabricating nano PdPtCuIn high-entropy intermetallic compound (c-PdPtCuIn-HEI) by laser liquid-phase ablation

[0047] (1) Add 50 mg of high-purity (99.9%) palladium, platinum, copper, and indium powders (particle size 10 nm - 1 μm) in a molar ratio of 4:1:2:3 to the prepared isopropanol-water mixed solution (volume ratio 3:1). The total volume of the solution is 50 mL. Then place the mixed solution in an open container device and ultrasonically disperse it evenly at room temperature for 10 min (ultrasonic frequency 40 kHz).

[0048] (2) Turn on the high-energy laser (Spectra-Physics Laser), use nanosecond lasers with a wavelength of 355 nm and a laser light guiding system. Set the focal length of the plano-convex lens to 500 mm and fix the lens 450 mm directly above the reaction container. Let the high-energy laser perform laser ablation treatment on the mixed solution in the container. The energy of the high-energy nanosecond laser is 100 mJ, the frequency is 50 Hz, and the irradiation time is 1 h. After the high-energy laser liquid-phase ablation, nano PdPtCuIn high-entropy intermetallic compound (c-PdPtCuIn-HEI) is obtained.

[0049] Comparative Example 2: A method for fabricating nano AgPtCuIn high-entropy intermetallic compound (AgPtCuIn-HEI) by temperature-field modulated laser liquid-phase ablation

[0050] (1) Add 50 mg of high-purity (99.9%) silver, platinum, copper, and indium powders (particle size 10 nm - 1 μm) in a molar ratio of 4:1:2:3 to the prepared isopropanol-water mixed solution (volume ratio 3:1). The total volume of the solution is 50 mL. Then place the mixed solution in an open container device and ultrasonically disperse it evenly at room temperature for 10 min (ultrasonic frequency 40 kHz).

[0051] (2) Turn on the high-energy laser (Spectra-Physics Laser), use nanosecond lasers with a wavelength of 355 nm and a laser light guiding system. Set the focal length of the plano-convex lens to 500 mm and fix the lens 450 mm directly above the reaction container. Let the high-energy laser perform laser ablation treatment on the mixed solution in the container. The energy of the high-energy nanosecond laser is 100 mJ, the frequency is 50 Hz, and the irradiation time is 1 h; monitor the solution temperature in real time during the laser action through a thermocouple, and always keep the solution cooling and heating through a water cooling device (Shanghai Yushen Instruments Co., Ltd., model DFY-5) (i.e., place the open container device in the water cooling device) so that the temperature always remains at 20 ± 0.2 °C. After the high-energy laser liquid-phase ablation, nano PdPtCuIn high-entropy intermetallic compound (AgPtCuIn-HEI) is obtained.

[0052] Experimental Example 1: Characteristics and Performance Analysis of Platinum Group High-Entropy Intermetallic Compounds

[0053] (1) Transmission Electron Microscopy (TEM) Analysis

[0054] Using the nano platinum group high-entropy intermetallic compounds prepared in Examples 1-2 as test samples, TEM analysis was carried out on them with a 300 kV transmission electron microscope (FEI Tecnai G2 F30, FEI Company, USA). The obtained TEM analysis results are as Figure 1-4 shown. It can be seen from Figure 1-2 that the nano platinum group high-entropy intermetallic compounds (PdPtCuIn-HEI and PdPtCuSnBi-HEI) prepared in Examples 1-2 are all spherical micro-nano particles with uniform size distribution, and the particle size is about 20 nm ± 5 nm. In contrast, Figure 3 for the nano platinum group high-entropy intermetallic compound (c-PdPtCuIn-HEI) obtained in Comparative Example 1 (without temperature field modulation), its morphology is spherical micro-nano particles with sizes ranging from 10 to 200 nm, and the crystallinity is poor; while in Comparative Example 2, the Pd element was replaced by Ag, and the obtained product (c-AgPtCuIn-HEI) was difficult to obtain an alloy phase and could not form spherical micro-nano particles( Figure 4 ).

[0055] (2) EDS (Energy Dispersive Spectrometer) Element Distribution Analysis

[0056] The EDS element distribution analysis of the nano platinum group high-entropy intermetallic compounds prepared in Examples 1-2 was carried out using the energy dispersive spectrometer equipped with a transmission electron microscope (FEI Tecnai G2 F30). Figure 5-6 Figure shows the EDS element distribution maps of the nano platinum group high-entropy intermetallic compounds in Examples 1-2. It can be clearly seen from the figure that the elements in the globular-like nano particles are uniformly mixed to form an intermetallic compound. Metal atoms form a plasma plume under the action of intense laser. The growth time of the plasma plume is extremely short, and then the plasma plume rapidly condenses to form nano high-entropy intermetallic compounds due to the rapid quenching effect in the liquid environment.

[0057] (3) Electrochemical Catalysis Performance Test

[0058] All electrochemical catalysis performance tests were carried out using a three-electrode system. The working electrode in the test was a glassy carbon electrode of the nano platinum group high-entropy intermetallic compound, the counter electrode was a graphite rod electrode, and the reference electrode was a silver / silver chloride electrode under acidic conditions and a mercury / mercuric oxide electrode under alkaline conditions. The electrolyte was 0.5 M sulfuric acid solution, or 0.1 M potassium hydroxide solution, or a mixed solution of 1 M potassium hydroxide and 0.5 M formate. Among them, the preparation method of the working electrode is as follows:

[0059] Weigh 4 mg of the nano platinum group high-entropy intermetallic compound of Example 1-2 or Comparative Example 1, or commercial Pt / C or commercial Pd black catalyst, add 780 μL of deionized water and 200 μL of isopropanol, and then add 20 μL of 5 wt% Nafion dispersion. After ultrasonic dispersion, take 4 μL of the prepared ink drop and place it on the surface of a polished glassy carbon electrode (diameter 3 mm), and let it dry naturally at room temperature to obtain a working electrode.

[0060] The electrocatalytic hydrogen evolution performance under acidic conditions was carried out in a 0.5 M sulfuric acid solution, and the test results are as Figure 7 shown, where the scanning rate of linear sweep voltammetry is 5 mV / s. It can be seen from Figure 7 the electrochemical performance diagram that under acidic conditions, the overpotential corresponding to commercial Pt / C at a current density of 10 mA·cm -2 is 33 mV, and the overpotential corresponding to a current density of 1000 mA·cm -2 is 600 mV; its electrocatalytic hydrogen evolution activity is much lower than that of the platinum group high-entropy intermetallic compound obtained by laser liquid-phase ablation under temperature field modulation. Among them, the overpotential corresponding to PdPtCuIn-HEI at a current density of 10 mA·cm -2 is 21 mV, and the overpotential corresponding to a current density of 1000 mA·cm -2 is 183 mV; in addition, the overpotential corresponding to PdPtCuSnBi-HEI at a current density of 10 mA·cm -2 is 29.5 mV, and the overpotential corresponding to a current density of 1000 mA·cm -2 is 352 mV. The above results show that the platinum group high-entropy intermetallic compound prepared by laser liquid-phase ablation under temperature field modulation exhibits far better catalytic activity than commercial Pt / C. In addition, we compared the electrocatalytic hydrogen evolution performance of the platinum group high-entropy intermetallic compound with and without temperature field modulation, as Figure 8 shown. The overpotentials of c-PdPtCuIn-HEI obtained without temperature field modulation at current densities of 10 and 1000 mA·cm -2 are 33 and 464 mV respectively, both of which are greater than those of the platinum group high-entropy intermetallic compound PdPtCuIn-HEI obtained by laser liquid-phase ablation under temperature field modulation, indicating that a platinum group high-entropy intermetallic compound with better performance is obtained by laser liquid-phase ablation under temperature field modulation.

[0061] The electrocatalytic oxygen reduction performance under alkaline conditions was carried out in a 0.1 M potassium hydroxide solution, and the test results are as Figure 9 shown, where the scanning rate of linear sweep voltammetry is 10 mV / s. It can be seen from Figure 9From the electrochemical performance diagram, it can be seen that under alkaline conditions, the current density of commercial Pt / C at 0.9 V vs. RHE is -0.87 mA·cm -2 , while the current density of the platinum group high-entropy intermetallic compound (PdPtCuSnBi-HEI) at 0.9 V vs. RHE is -2.62 mA·cm -2 . At the same potential, the current density of PdPtCuSnBi-HEI is 3 times that of commercial Pt / C, and the current density of PdPtCuIn-HEI at 0.9 V vs. RHE is -3.20 mA·cm -2 , which is 3.6 times that of commercial Pt / C, indicating that the platinum group high-entropy intermetallic compounds exhibit better catalytic activity than commercial Pt / C.

[0062] The electrocatalytic formic acid oxidation performance under alkaline conditions was carried out in a mixed solution of 1 M potassium hydroxide and 0.5 M potassium formate, and the test results are as Figure 10 shown, where the scanning rate of cyclic voltammetry is 50 mV / s. From Figure 10 the electrochemical performance diagram, it can be seen that under alkaline conditions, the limiting current density of commercial palladium black is 0.74 A·mg Pd -1 , and the limiting current density of the platinum group high-entropy intermetallic compound PdPtCuIn-HEI is 3.74 A·mg Pd -1 , while the limiting current density of PdPtCuSnBi-HEI is 4.5 A·mg Pd -1 . The limiting current density of PdPtCuIn-HEI is 5 times that of commercial palladium black, and the limiting current density of PdPtCuSnBi-HEI is 6 times that of commercial palladium black, indicating that it has far better catalytic activity than commercial palladium black.

[0063] In summary, under the modulation of the temperature field, uniformly distributed nano platinum group high-entropy intermetallic compounds are formed after the action of high-energy laser in the liquid. The platinum group high-entropy intermetallic compounds prepared by this method can further optimize the electronic structure through the synergistic effect of multi-metal atoms and the ordered atomic configuration, thereby improving their catalytic activity. On the one hand, the high-entropy intermetallic compounds have an ordered atomic structure, which promotes the separation of active sites and the electronic structure can be regulated, avoiding the inactivation of the catalyst caused by the aggregation of active sites. On the other hand, due to its ordered atomic configuration, the catalyst can better resist the influence of the external environment during the electrochemical reaction process and maintain the integrity of the structure.

[0064] The above has described the embodiments of the present invention in detail, but the present invention is not limited to the described embodiments. For those skilled in the art, without departing from the principle and spirit of the present invention, various changes, modifications, substitutions, and variations made to these embodiments still fall within the protection scope of the present invention.

Claims

1. A method for manufacturing nano-platinum group high entropy intermetallic compounds by temperature field modulated laser liquid phase ablation, characterized in that: At least four metal elements including platinum group metal elements, transition metal elements and main group metal elements are used as matrix materials, which are mixed with a solvent to form a powder suspension or pressed into a metal target material after mixing and fixed in a solvent. Then, laser liquid phase ablation is used under temperature field modulation to perform laser ablation treatment on the micro-nano powder in the suspension or the metal target material in the solvent at a constant temperature, so that a plasma plume is formed under the action of temperature field modulated laser liquid phase ablation, and the plasma plume rapidly condenses due to the rapid quenching effect, thereby preparing a platinum group nano high entropy metal compound.

2. The method for manufacturing nano-platinum group high entropy intermetallic compounds by temperature field modulated laser liquid phase ablation according to claim 1, characterized in that: The following steps are involved: S1. Add at least four metal elements including platinum group metal elements, transition metal elements and main group metal elements into a solvent, mix them and make a powder suspension; or press at least four metal elements including platinum group metal elements, transition metal elements and main group metal elements into a metal target, and then fix them in a solvent; S2. Place the powder suspension or metal target of S1 under a controllable temperature field, and then use a high-frequency and high-energy laser to perform laser ablation on the micro-nano powder in the suspension or the metal target in the solvent at a constant temperature in the range of 20-30°C to prepare a platinum group nano high-entropy metal compound.

3. The method for manufacturing nano-platinum group high entropy intermetallic compounds by temperature field modulated laser liquid phase ablation according to claim 2, characterized in that: The platinum group metal elements include palladium and platinum, the transition metal element is copper, and the main group metal elements are indium or tin and bismuth.

4. The method for manufacturing nano-platinum group high entropy intermetallic compounds by temperature field modulated laser liquid phase ablation according to claim 2, characterized in that: The solvent is water or a mixture of an organic solvent and water, and the organic solvent includes isopropanol, ethanol, and acetone.

5. The method for manufacturing nano-platinum group high entropy intermetallic compounds by temperature field modulated laser liquid phase ablation according to claim 2, characterized in that: The particle size of the micro-nano powder in S2 is 10nm-1μm.

6. The method for manufacturing nano-platinum group high entropy intermetallic compounds by temperature field modulated laser liquid phase ablation according to claim 2, characterized in that: The pulse laser energy required for the laser ablation process is 100uJ-1000mJ, the frequency is 1-2000Hz, and the action time is 10min-6h.

7. The method for manufacturing nano-platinum group high entropy intermetallic compounds by temperature field modulated laser liquid phase ablation according to claim 2, characterized in that: The laser ablation process uses a 355nm-1064nm nanosecond laser and a 355nm-1064nm laser light guide system, or a 355nm-1064nm picosecond laser and a 355nm-1064nm laser light guide system.

8. A nano-platinum group high entropy intermetallic compound prepared by the preparation method according to any one of claims 1 to 7.

9. Application of the nano-platinum group high entropy intermetallic compound according to claim 8 in the field of electrocatalysis.

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